A well treatment microemulsion includes an oil external phase, an internal aqueous phase and a hydrophilic surfactant. The surfactant has a hydrophile lipophile balance of between 8-18. The oil external phase may include d-Limonene, xylenes, light mineral oil, or kerosene. The surfactant is configured to emulsify the water of the internal aqueous phase into the oil of the external (continuous) phase. The surfactant may include polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate or mixtures therebetween. The use of hydrophilic surfactants to emulsify an internal aqueous phase within an oil external microemulsion produces unexpected and beneficial results.
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1. A well treatment microemulsion comprising:
an oil external phase;
an internal aqueous phase; and
a surfactant or a surfactant mixture configured to emulsify the aqueous phase within the oil phase, wherein the surfactant or the surfactant mixture has a hydrophile lipophile balance of between 10-18, wherein the surfactant or the surfactant mixture comprises a surfactant component selected from the group consisting of ethoxylated castor oil comprising 25-45 moles of ethylene oxide, ethoxylated alcohols comprising 5-20 moles of ethylene oxide, ethoxylated amides comprising 5-20 moles of ethylene oxide, ethoxylated fatty acids comprising 5-20 moles of ethylene oxide and combinations thereof.
2. The well treatment microemulsion of
3. The well treatment microemulsion of
4. The well treatment microemulsion of
5. The well treatment microemulsion of
6. The well treatment microemulsion of
7. The well treatment microemulsion of
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This application is a continuation of U.S. patent application Ser. No. 12/618,535, filed Nov. 13, 2009, entitled “Water-in-Oil Microemulsions for Oilfield Applications”, which claims the benefit of U.S. Provisional Patent Application Ser. No. 61/114,125, filed Nov. 13, 2008, entitled “Water-in-Oil Microemulsions for Oilfield Applications”, the disclosure of which are herein incorporated by reference.
The present invention generally relates to the production of petroleum and more particularly to compositions and processes for improving the recovery of petroleum from a subterranean geological formation.
For many years, petroleum has been recovered from subterranean reservoirs through the use of drilled wells and production equipment. During the production of desirable hydrocarbons, such as crude oil and natural gas, a number of other naturally occurring substances may also be encountered within the subterranean environment.
Many undesirable downhole products must be managed during the production of hydrocarbons. For example, scale, paraffins, fines, sulfur, heavy oil tar by-products, hydrogen sulfide, and water blocks commonly accumulate in and around the formation, well casing, production tubing and recovery equipment. Alternatively, it may be necessary to remove injected fluids from the near wellbore area, such as drilling fluids, cement filtrate, kill fluids, polymers and water blocks. To maintain an efficient recovery of petroleum, it is frequently necessary to clean or remove these accumulations and deposits.
The removal of unwanted deposits from the wellbore and production equipment is generally referred to as “remediation.” In contrast, the term “stimulation” generally refers to the treatment of geological formations to improve the recovery of hydrocarbons. Common stimulation techniques include well fracturing and acidizing operations. Well remediation and stimulation are important services that are offered through a variety of techniques by a large number of companies.
The effectiveness of well remediation and stimulation operations is greatly affected by the chemical agents used during these services. Operators have discovered that microemulsions can offer an advantageous vehicle for delivering solvents or other treatment chemicals to a targeted treatment area. Microemulsions are characterized as either water-in-oil (an aqueous phase is dispersed in an oil phase) or oil-in-water (an oil phase dispersed in an aqueous phase) mixtures. Microemulsions comprise droplets having a diameter in the range of about 1-100 nm. These systems appear clear or transparent to the human eye compared to conventional emulsion systems which have droplet sizes>400 nm in diameter and a cloudy appearance. Microemulsions are thermodynamically stable and exhibit no phase separation.
The separation of the oil and water phases depends on the creation of an interface of surfactant molecules between the water and oil molecules. Nonionic surfactants are often classified according to the hydrophile-lipophile balance (HLB) system. The HLB value of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic, determined by calculating values for the different regions of the molecule. Originally, the HLB value was defined as a relative measure of the ratio of the weight percent ethylene oxide (EO) in a given nonionic surfactant.
Surfactants with lower HLB values are typically used for making oil-external (water-in-oil) microemulsions, while surfactants with higher HLB values are used for making water external (oil-in-water) microemulsions.
The prior art includes many examples that show that surfactants with an HLB generally greater than about 8 will produce oil-in-water emulsions, while surfactants with an HLB of about 3 to 8 will produce water-in-oil emulsions.
U.S. Pat. No. 7,380,606 (Pursley, et al.; Jun. 3, 2008) titled “Composition and Process for Well Cleaning” states that water-in-oil microemulsions should be prepared using surfactants with an HLB value of between 3 and 8, while oil-in-water microemulsions are prepared with surfactants having an HLB of 8 to 18.
An article by D. F. Brost and J. Silveira titled, “Surfactants Assist Water-in-Oil Monitoring by Fluorescence” in the October 2008 online issue of World Oil states, “Surfactants with an HLB less than 10 stabilize water-in-oil emulsions. Surfactants with an HLB greater than 10 stabilize oil-in-water emulsions. Within that group, surfactants with an HLB of 12-15 act as detergents and are commonly used to remove oil from solid surfaces.”
U.S. Pat. No. 3,919,411 titled, “Injectible Adjuvant and Compositions Including Such Adjuvant”, Nov. 11, 1975 by Glass, et al. states, “Where surfactants are used for dispersing oil in water, the final HLB number should be above 6. In the case where surfactants are used of the type for dispersing water in oil, the final HLB number should be below 6.”
In a presentation given to the Midwest Chapter of the Society of Cosmetic Chemists in 2004, Uniqema reported that for making water-in-oil emulsions, surfactants with HLBs of 4-6 should be chosen, while surfactants with HLBs of 8-16 should be used when making oil-in-water emulsions.
In direct contrast to the prior art, the present invention describes the surprising discovery that high HLB surfactants can be used to produce water-in-oil microemulsions that find use in oilfield and well treatment applications.
Although a number of compounds and techniques are known in the prior art, there is a continued need for more effective microemulsions for remediation stimulation services. There is a particular need to identify new surfactants and surfactant mixtures that can be used to prepare stable microemulsions.
In preferred embodiments, a well treatment microemulsion includes an oil external phase, an internal aqueous phase and a surfactant. The surfactant has a hydrophile lipophile balance of between 8-18. The oil external phase may include but is not necessarily limited to d-Limonene, xylenes, light mineral oil, or kerosene. The surfactant is configured to emulsify the water of the internal aqueous phase into the oil of the external (continuous) phase. Suitable surfactants may include but are not necessarily limited to polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate or mixtures therebetween.
In preferred embodiments, the present invention relates to the preparation of an oil external microemulsion, using a high HLB surfactant or surfactant mixture. It is well known that when two or more surfactants are mixed together, the HLB of the resulting combination is a weighted average of the HLBs of each of the components of the surfactant mixture. This HLB is reported simply as the average HLB. Select surfactants and surfactant mixtures with high HLB values have been discovered to emulsify water in a hydrocarbon oil phase. The use of a high HLB surfactant or surfactant mixture provides a new range of surfactants that have not previously been used in oil external microemulsions. In a presently preferred embodiment, the well treatment microemulsion includes an oil external (continuous) phase, an aqueous internal (dispersed) phase, and a surfactant component. The water-in-oil microemulsion may also include an alcohol component. The aqueous phase is preferably formed with water.
The oil external phase preferably consists of a hydrocarbon terpene or mixture of hydrocarbon terpenes. In preferred embodiments, the oil external phase is formed by using terpene hydrocarbons derived from citrus, pine, eucalyptus, peppermint or other sources. In a particularly preferred embodiment, the oil external phase is prepared using d-Limonene (CAS #94266-47-4; citrus terpenes). d-Limonene is commercially available from a variety of sources and is characterized as a biodegradable solvent. In alternate preferred embodiments, the oil external phase is prepared from a mixture of terpene hydrocarbons. In yet another preferred embodiment, the oil external phase is prepared from non-terpene hydrocarbons, such as xylenes, paraffin oil, a mixture of cycloparaffinic and isoparaffinic hydrocarbon, and mineral oil.
In a preferred embodiment, the surfactant component is selected as a nonionic surfactant or surfactant mixture having an HLB value of between 8 and 18. In a more particularly preferred embodiment, the selected surfactant or surfactant mixture has an HLB value of between 10 and 17.
In a particularly preferred embodiment, the surfactant component is an ethoxylated alcohol. In a more preferred embodiment, the surfactant component is an ethoxylated C8-C18 alcohol. In a still more preferred embodiment, the surfactant component is an ethoxylated C8-C18 alcohol with 5-20 moles of ethylene oxide (EO).
In a particularly preferred embodiment, the surfactant component is an ethoxylated vegetable oil. In a more preferred embodiment, the surfactant component is an ethoxylated castor oil. In a still more preferred embodiment, the surfactant component is an ethoxylated castor oil with 25-45 moles of EO.
In a particularly preferred embodiment, the surfactant component is an ethoxylated amide. In a more preferred embodiment, the surfactant component is an ethoxylated C8-C18 amide. In a still more preferred embodiment, the surfactant component is an ethoxylated C8-C18 amide with 5-20 moles of EO.
In another particularly preferred embodiment, the surfactant component is an ethoxylated fatty acid. In a more preferred embodiment, the surfactant component is an ethoxylated C8-C18 fatty acid. In a still more preferred embodiment, the surfactant component is an ethoxylated C8-C18 fatty acid with 5-20 moles of EO.
In another preferred embodiment, the surfactant component is a polyoxyethylene fatty glyceride or a polyoxyethylene hydrogenated castor oil (ethoxylated castor oil).
In another preferred embodiment, the surfactant component is a polyoxyethylene sorbitan ester. In a more preferred embodiment, the surfactant component is a polyoxyethylene sorbitan monoester. In a still more preferred embodiment, the surfactant component is a polyoxyethylene sorbitan monooleate.
In another particularly preferred embodiment, the surfactant component is a combination of two or more of the following: ethoxylated alcohol, ethoxylated vegetable oil, ethoxylated amide, ethoxylated fatty acid, polyoxyethylene fatty glyceride, and polyoxyethylene sorbitan ester. In a more preferred embodiment, the surfactant component is a combination of two or more of the following: ethoxylated C8-C18 alcohol, ethoxylated castor oil, ethoxylated C8-C18 amide, ethoxylated C8-C18 fatty acid, polyoxyethylene fatty glyceride, and polyoxyethylene sorbitan monoester. In a still more preferred embodiment, the surfactant component is a combination of two or more of the following: ethoxylated C8-C18 alcohol with 5-20 moles of EO, ethoxylated castor oil with 25-45 moles of EO, ethoxylated C8-C18 amide with 5-20 moles of EO, ethoxylated C8-C18 fatty acid with 5-20 moles of EO, polyoxyethylene fatty glyceride, and polyoxyethylene sorbitan monooleate. In alternate preferred embodiments, other nonionic surfactants can be included with these combinations, as long as the HLB of the surfactant mixture is between 8 and 18. For example, sorbitan monooleate (HLB 4.3) can be included with one or more nonionic surfactants to create a suitable surfactant combination having an HLB between 8 and at least 11.
Some examples of surfactants that have been successfully used to create oil-external microemulsions include Stepantex CO-30 (ethoxylated castor oil with 30 moles of EO, sold by Stepan Company), Tomadol 91-6 (ethoxylated C9-C11 alcohol with 6 moles of EO, sold by Air Products), Biosoft N91-6 (ethoxylated C9-C11 alcohol with 6 moles of EO, sold by Stepan Company), Tween 20 (polyoxyethylene sorbitan monolaurate, sold by Croda USA), Tween 40 (polyoxyethylene sorbitan monopalmitate, sold by Croda USA), Tween 60 (polyoxyethylene sorbitan monostearate, sold by Croda USA), Tween (polyoxyethylene sorbitan tristearate, sold by Croda USA), Tween 80 (polyoxyethylene sorbitan monooleate, sold by Croda USA), Tween 81 (polyoxyethylene sorbitan monooleate, sold by Croda USA), a combination of Span 80 (sorbitan monooleate) and Cirrasol G-1292 Special (polyoxyethylene fatty glyceride; both sold by Croda USA), and Biosoft N1-9 (ethoxylated C11 alcohol with 9 moles of EO, sold by Stepan Company). It should be noted that surfactants and mixtures of surfactants (also known as “surfactant packages”) often contain ingredients in addition to the specified surface active agents. These ingredients can vary from supplier to supplier, and may even vary within a particular supplier, as long as the resulting surfactant or surfactant package meets certain performance requirements and/or physical specifications. These ingredients may include normal product variations due to the manufacturing processes of the surfactant or surfactant package, and they may also include materials that are naturally introduced by the source feedstock. Other ingredients may be intentionally added to the surfactant or surfactant package. These ingredients include, but are not limited to, stabilizers, modifiers, solvents, antioxidants, dispersants, solubilizers, handling aids, physical property modifiers, and the like.
In yet another alternate preferred embodiment, the surfactant component selected is an anionic surfactant, including but not limited to sulfonates, specifically internal olefin sulfonates and linear alkylbenzene sulfonates. Presently preferred anionic surfactants include C15-C18 internal olefin sulfonates (available as Petrostep S2, sold by Stepan Company) and linear alkylbenzene sulfonate/linear sodium dodecylbenzene sulfonates (available as Polystep LAS-50, sold by Stepan Company).
In yet another alternate preferred embodiment, the surfactant component is selected as a combination of nonionic and anionic surfactants, such as but not limited to ethoxylated alcohols, ethoxylated castor oil, and sulfonates. Presently preferred nonionic/anionic surfactant combinations comprise ethoxylated C8-C18 alcohol with 5-20 moles EO, ethoxylated castor oil with 25-45 moles of EO, and C15-C18 internal olefin sulfonates.
The alcohol molecules of the well treatment microemulsion stabilize the microemulsion through interactions at the water and oil interface, thereby further stabilizing the microemulsion. The alcohol also lowers the freezing point of the well treatment microemulsion. Although isopropanol is presently preferred, alternative suitable alcohols include midrange primary, secondary and tertiary alcohols with between 1 and 20 carbon atoms, such as ethanol, t-butanol, n-butanol, n-pentanol, n-hexanol and 2-ethyl-hexanol. Other freeze prevention additives can additionally or alternatively be added, such as detergent range alcohols ethoxylate, ethylene glycols (EG), polyethylene glycols (PEG), propylene glycols (PG) and triethylene glycols (TEG), with triethylene glycol being presently preferred.
In preferred embodiments, the well treatment microemulsion comprises 30-60% by weight terpene mixture or non-terpene hydrocarbons (oil phase), 25-50% by weight surfactant or surfactant mixture (surfactant component), 5-30% by weight water (aqueous phase), 0-3% by weight TEG (alcohol) and 0-35% isopropyl alcohol (alcohol). Using the various components identified above, the following preferred well treatment microemulsion formulations can be prepared.
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant mixture. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 9.64% by weight isopropanol (alcohol), about 1.36% by weight triethylene glycol (alcohol), and about 32.8% by weight surfactant mixture having an average HLB of about 10 and comprising the following surfactants: (i) polyoxyethylene castor oil (Cirrasol G-1292 Special, sold by Croda USA) and (ii) sorbitan monooleate (Span 80, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 35.8% by weight d-Limonene (external oil phase), about 9.4% by weight water (dispersed aqueous phase), about 32.4% by weight isopropanol (alcohol), about 1.6% by weight triethylene glycol (alcohol), and about 20.8% by weight surfactant having an HLB of about 10 and comprising the following surfactant: polyoxyethylene sorbitan monooleate (Tween 81, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant mixture. The well treatment microemulsion contains about 41.8% by weight xylenes (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 9.64% by weight isopropanol (alcohol), 1.36% by weight triethylene glycol (alcohol), and about 32.8% by weight surfactant mixture having an average HLB of about 10 and comprising the following surfactants: (i) polyoxyethylene fatty glyceride (Cirrasol G-1292 Special, sold by Croda USA) and (ii) sorbitan monooleate (Span 80, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohol and a surfactant mixture. The well treatment microemulsion contains about 43% by weight of light mineral oil (external oil phase), about 10% by weight water (dispersed aqueous phase), about 11% by weight isopropanol (alcohol), and about 36% by weight of a surfactant mixture having an average HLB of about 10 and comprising the following surfactants: sorbitan monooleate (Span 80, sold by Croda USA) and polyoxyethylene sorbitan monooleate (Tween 80, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 35.8% by weight d-Limonene (external oil phase), about 9.4% by weight water (dispersed aqueous phase), about 32.4% by weight isopropanol (alcohol), about 1.6% by weight triethylene glycol (alcohol), and about 20.8% by weight surfactant having an HLB of about 10.5 and comprising the following surfactant: polyoxyethylene sorbitan tristearate (Tween 65, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 9.64% by weight isopropanol (alcohol), about 1.36% by weight triethylene glycol (alcohol), and about 32.8% by weight surfactant having an HLB of about 10.8 and comprising the following surfactant: polyoxyethylene fatty glyceride (Cirrasol G-1292 Special, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant package. The well treatment microemulsion contains about 41.8% by weight terpene hydrocarbon mixture-1 (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 1.6% by weight triethylene glycol (alcohol), about 6.4% by weight isopropanol (alcohol), and about 35.8% by weight surfactant mixture having an HLB of about 12.5 and comprising the following surfactant: ethoxylated C9-C11 alcohol with 6 moles EO (Tomadol 91-6, sold by Air Products).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant package. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 1.6% by weight triethylene glycol (alcohol), about 6.4% by weight isopropanol (alcohol), and about 35.8% by weight surfactant mixture having an average HLB of about 12.8 and comprising the following surfactants: (i) ethoxylated castor oil with 25-45 moles of EO and (ii) ethoxylated C8-C18 alcohol with 5-20 moles EO.
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant package. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 1.6% by weight triethylene glycol (alcohol), about 6.4% by weight isopropanol (alcohol), and about 35.8% by weight surfactant having an HLB of about 13 and comprising the following surfactant: ethoxylated castor oil with 30 moles of EO (Stepantex CO 30, sold by Stepan Company).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant mixture. The well treatment microemulsion contains about 41.8% by weight d-Limonene (oil phase), about 14.4% by weight water (aqueous phase), about 1.6% by weight triethylene glycol (alcohol), about 6.4% by weight isopropanol (alcohol), and about 35.8% by weight surfactant mixture having an average HLB of about 13.1 and comprising the following surfactants: (i) ethoxylated C8-C18 amide with 5-20 moles of EO; (ii) ethoxylated castor oil with 25-45 moles of EO; and (iii) ethoxylated C8-C18 fatty acid with 5-20 moles of EO. Tables 1 and 2 below provides the thermal analysis and solubility tests, respectively, of the well treatment microemulsion of Example 10.
TABLE 1
Thermal Analysis of Oil External Microemulsion
Temperature
Time
Observation
Stability
72 F.
≥24 hr
Clear
Homogenous/1 phase
120 F.
≥24 hr
Clear
Homogenous/1 phase
TABLE 2
Solubility Tests of Oil External Microemulsion
Condensate
Isopar L
d-Limonene
Water
Soluble
Soluble
Soluble
Insoluble
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant mixture. The well treatment microemulsion contains about 44.7% by weight citrus pine terpene-hydrocarbon mixture-1 (external oil phase), about 15.4% by weight water (dispersed aqueous phase), about 1.7% by weight triethylene glycol (alcohol), and about 38.2% by weight surfactant mixture having an average HLB of about 13.1 and comprising the following surfactants: (i) ethoxylated C8-C18 amide with 5-20 moles of EO; (ii) ethoxylated castor oil with 25-45 moles of EO; and (iii) ethoxylated C8-C18 fatty acid with 5-20 moles of EO.
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant mixture. The well treatment microemulsion contains about 44.7% by weight citrus pine terpene-hydrocarbon mixture-2 (external oil phase), about 15.4% by weight water (dispersed aqueous phase), about 1.7% by weight triethylene glycol (alcohol), and about 38.2% by weight surfactant mixture having an average HLB of about 13.1 and comprising the following surfactants: (i) ethoxylated C8-C18 amide with 5-20 moles of EO; (ii) ethoxylated castor oil with 25-45 moles of EO; and (iii) ethoxylated C8-C18 fatty acid with 5-20 moles of EO.
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 6.4% by weight isopropanol (alcohol), about 1.6% by weight triethylene glycol (alcohol), and about 35.8% by weight surfactant having an HLB of about 13.9 comprising the following surfactant: ethoxylated C11 alcohol with 9 moles EO (Biosoft N1-9, sold by Stepan Company).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 6.4% by weight isopropanol (alcohol), about 1.6% by weight triethylene glycol (alcohol), and about 35.8% by weight surfactant having an HLB of about 14.9 and comprising the following surfactant: polyoxyethylene sorbitan monostearate (Tween 60, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohol and a surfactant. The well treatment microemulsion contains about 40.2% by weight of a mixture of Conosol 145 (external oil phase comprised of cycloparaffinic and isoparaffinic hydrocarbons, sold by Calumet Specialty Products Partners), about 13.8% by weight water (dispersed aqueous phase), about 6.2% by weight isopropanol (alcohol), and about 39.8% by weight surfactant having an HLB of about 14.9 and comprising the surfactant: polyoxyethylene sorbitan monostearate (Tween 60, sold by Croda US).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 9.64% by weight isopropanol (alcohol), about 1.36% by weight triethylene glycol (alcohol), and about 32.8% by weight surfactant having an HLB of about 15 and comprising the following surfactant: polyoxyethylene sorbitan monooleate (Tween 80, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohol and a surfactant. The well treatment microemulsion contains about 42.5% by weight of kerosene (external oil phase), about 10.6% by weight water (dispersed aqueous phase), about 6.5% by weight tertiary butanol (alcohol), and about 40.4% by weight of a surfactant with an HLB of about 15 and comprising the following surfactant: polyoxyethylene sorbitan monooleate (Tween 80, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion can be made with aromatic comprising hydrocarbons. An example includes about 41.8% by weight xylenes (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 9.64% by weight isopropanol (alcohol), 1.36% by weight triethylene glycol (alcohol), and about 32.8% by weight surfactant having an HLB of about 15 and comprising the following surfactant: polyoxyethylene sorbitan monooleate (Tween 80, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 6.4% by weight isopropanol (alcohol), about 1.6% by weight triethylene glycol (alcohol), and about 35.8% by weight surfactant having an HLB of about 15.6 and comprising the following surfactant: polyoxyethylene sorbitan monopalmitate (Tween 40, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 6.4% by weight isopropanol (alcohol), about 1.6% by weight triethylene glycol (alcohol), and about 35.8% by weight surfactant having an HLB of about 16.7 and comprising the following surfactant: polyoxyethylene sorbitan monolaurate (Tween 20, sold by Croda USA).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 44.7% by weight d-Limonene (external oil phase), about 15.4% by weight water (dispersed aqueous phase), about 1.7% by weight triethylene glycol (alcohol), and about 38.2% by weight anionic surfactant comprising a linear sodium dodecylbenzene sulfonate (Polystep LAS-50, sold by Stepan Company).
An oil-external well treatment microemulsion includes a continuous oil phase, a dispersed water phase, alcohols and a surfactant. The well treatment microemulsion contains about 41.8% by weight d-Limonene (external oil phase), about 14.4% by weight water (dispersed aqueous phase), about 6.4% by weight isopropanol (alcohol), about 1.6% by weight triethylene glycol (alcohol), and about 35.8% by weight of a surfactant mixture comprising: (i) ethoxylated castor oil with 25-45 moles of EO, (ii) ethoxylated C8-C18 alcohol with 5-20 moles EO (iii), and an anionic surfactant comprising a C15-C18 internal olefin sulfonate (Petrostep S2, sold by Stepan Company).
Although for the purposes of the present disclosure preferred embodiments of the well treatment microemulsions are described in connection with well remediation, stimulation, acidizing operations, drilling operations and hydrogen sulfide mitigation applications, it will be understood that the inventive well treatment microemulsions can be used in additional, alternative applications. For example, it is contemplated that the well treatment microemulsion could also be used to clean surface equipment and downhole equipment.
In well remediation applications, the selected well treatment microemulsion is preferably injected directly into the wellbore through the production tubing or through the use of coiled tubing or similar delivery mechanisms. Once downhole, the well treatment microemulsion remedies drilling damage, fracturing fluid damage, water blocks and removes fines, asphaltenes and paraffins from the formation and wellbore. The well treatment microemulsion also serves to thin heavy hydrocarbons, alleviate water blocks and lower pore pressure in the formation.
During drilling operations, the well treatment microemulsions can be added to drilling fluids and injected into the wellbore through the drill string. The well treatment microemulsion is effective at removing fines and debris from the wellbore created by the drilling process.
The inventive well treatment microemulsions can also be used in stimulation operations.
The well treatment microemulsions can also be used to deliver acids during acidizing operations. Acids commonly used include hydrochloric, acetic, formic, and hydrochloric-hydrofluoric acids. In a presently preferred embodiment, the selected microemulsion is combined with an acidified carrier fluid to prepare a microemulsion suitable for acidizing operations.
As mentioned above, the inventive microemulsions can also be used for hydrogen sulfide mitigation. In preferred embodiments, the well treatment microemulsions are injected into the wellbore so that escaping hydrogen sulfide gas is “stripped” through the well treatment microemulsions. Preferably, the inventive microemulsion is periodically injected into problem wells to mitigate hydrogen sulfide production. Alternatively, the microemulsion can be injected downhole via capillary tubing on a continuous basis. In yet another alternate embodiment, the well treatment microemulsion can be placed in a container that is placed in fluid communication with the hydrogen sulfide.
It is clear that the present invention is well adapted to carry out its objectives and attain the ends and advantages mentioned above as well as those inherent therein. While presently preferred embodiments of the invention have been described in varying detail for purposes of disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art and which are encompassed within the scope of the appended claims and within the spirit of the invention disclosed in the written description.
Champagne, Lakia M., Morrison, David S.
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| 11034879, | Mar 14 2013 | Flotek Chemistry, LLC | Methods and compositions for use in oil and/or gas wells |
| 11053433, | Dec 01 2017 | Flotek Chemistry, LLC | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
| 11104843, | Oct 10 2019 | Flotek Chemistry, LLC | Well treatment compositions and methods comprising certain microemulsions and certain clay control additives exhibiting synergistic effect of enhancing clay swelling protection and persistency |
| 11180690, | Mar 14 2013 | Flotek Chemistry, LLC | Diluted microemulsions with low surface tensions |
| 11254856, | Mar 14 2013 | Flotek Chemistry, LLC | Methods and compositions for use in oil and/or gas wells |
| 11407930, | May 08 2012 | Flotek Chemistry, LLC | Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons |
| 11473004, | Dec 02 2016 | UNIVERSITY OF WYOMING | Microemulsions and uses thereof to displace oil in heterogeneous porous media |
| 11512243, | Oct 23 2020 | Flotek Chemistry, LLC | Microemulsions comprising an alkyl propoxylated sulfate surfactant, and related methods |
| 11560351, | Mar 14 2013 | Flotek Chemistry, LLC | Methods and compositions incorporating alkyl polyglycoside surfactant for use in oil and/or gas wells |
| 11591510, | Apr 07 2022 | Halliburton Energy Services, Inc. | Wellbore cleaner for use in displacement trains |
| 11597873, | Oct 10 2019 | Flotek Chemistry, LLC | Well treatment compositions and methods comprising certain microemulsions and certain clay control additives exhibiting synergistic effect of enhancing clay swelling protection and persistency |
| 11634625, | Mar 14 2013 | Flotek Chemistry, LLC | Siloxane surfactant additives for oil and gas applications |
| 11787996, | Jun 07 2022 | Halliburton Energy Services, Inc. | Wellbore cleaner for use in displacement trains |
| Patent | Priority | Assignee | Title |
| 3047062, | |||
| 3060210, | |||
| 3347789, | |||
| 3368624, | |||
| 3483923, | |||
| 3710865, | |||
| 3756319, | |||
| 3760881, | |||
| 3850248, | |||
| 3919411, | |||
| 4005020, | Jul 19 1973 | Petrolite Corporation | Paraffin removing compositions |
| 4206809, | Nov 02 1978 | MARATHON OIL COMPANY, AN OH CORP | Slug design in micellar-polymer flooding |
| 4233165, | May 24 1978 | Exxon Production Research Company | Well treatment with emulsion dispersions |
| 4276935, | Oct 30 1979 | Phillips Petroleum Company | Treatment of subsurface gas-bearing formations to reduce water production therefrom |
| 4360061, | Apr 03 1980 | Exxon Research and Engineering Co. | Oil recovery process using polymer microemulsion complexes |
| 4414128, | Jun 08 1981 | Procter & Gamble Company, The | Liquid detergent compositions |
| 4472291, | Mar 07 1983 | High viscosity microemulsions | |
| 4511488, | Dec 05 1983 | Penetone Corporation | D-Limonene based aqueous cleaning compositions |
| 4650000, | Nov 07 1984 | Berol Kemi AB; TENDEX KJEMISERVICE A S | Acidizing method using microemulsion |
| 4844756, | Dec 06 1985 | LUBRIZOL CORPORATION, THE, 29400 LAKELAND BLVD , WICKLIFFE, OH 44092, AN OH CORP | Water-in-oil emulsions |
| 5008026, | Jan 30 1989 | HALLIBURTON COMPANY, A CORP OF DELAWARE | Well treatment compositions and method |
| 5034140, | Nov 27 1989 | Halliburton Company | Well acidizing compositions and method |
| 5076954, | Aug 14 1987 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
| 5083613, | Nov 24 1986 | CANADIAN OCCIDENTAL PETROLEUM LTD | Process for producing bitumen |
| 5095989, | Feb 21 1991 | Texaco Inc.; TEXACO INC , 2000 WESTCHESTER AVENUE, WHITE PLAINS, NY 10650 A CORP OF DELAWARE; TEXACO DEVELOPMENT CORPORATION, 2000 WESTCHESTER AVENUE, WHITE PLAINS, NY 10650 A CORP OF DELAWARE | Microemulsion method for improving the injectivity of a well |
| 5217531, | Dec 23 1991 | BJ SERVICES COMPANY, U S A | Fluid loss additives for cementing compositions |
| 5247995, | Feb 26 1992 | BJ Services Company | Method of dissolving organic filter cake obtained from polysaccharide based fluids used in production operations and completions of oil and gas wells |
| 5310002, | Apr 17 1992 | Halliburton Company | Gas well treatment compositions and methods |
| 5356482, | Dec 10 1991 | PSC Industrial Outsourcing, LP | Process for vessel decontamination |
| 5567675, | Feb 16 1994 | BUCKMAN LABORATORIES INTERNATIONAL, INC | Application of N,N-dialkylamides to control the formation of emulsions or sludge during drilling or workover of producing oil wells |
| 5587354, | Sep 25 1992 | Integrity Industries, Inc. | Drilling fluid and drilling fluid additive |
| 5587357, | Sep 09 1994 | Colgate-Palmolive Co. | Liquid cleaning compositions |
| 5604195, | Nov 23 1993 | Colgate-Palmolive Company | Liquid cleaning compositions with polyethylene glycol grease release agent |
| 5652200, | May 07 1993 | Schlumberger Technology Corporation | Water based drilling fluid additive and methods of using fluids containing additives |
| 5665689, | Sep 04 1996 | Colgate-Palmolive Co. | Cleaning compositions comprising mixtures of partially esterified full esterified and non-esterfied ethoxylated polyhydric alcohols and N-alkyl aldonamides |
| 5676763, | Jun 07 1995 | EXPRESS CHEMICAL FINANCE, LLC | Process for cleaning pipe dope and other solids from well systems |
| 5697458, | May 02 1996 | ZABALA, ENRIQUE; INTEGRATED PETROLEUM SERVICES,CA | Drilling fluid process |
| 5707940, | Jun 07 1995 | The Lubrizol Corporation; LUBRIZOL CORPORATION, THE | Environmentally friendly water based drilling fluids |
| 5762138, | Dec 09 1996 | Halliburton Energy Services, Inc | Method of preventing incompatibility between aqueous well treating fluids and hydrocarbons |
| 5784386, | Jul 03 1996 | McData Services Corporation | Fault tolerant synchronous clock distribution |
| 5811383, | Apr 02 1993 | The Dow Chemical Company | High water content, low viscosity, oil continuous microemulsions and emulsions, and their use in cleaning applications |
| 5830831, | May 11 1995 | ConocoPhillips Company | Surfactant blends for well operations |
| 5874386, | Feb 13 1998 | ConocoPhillips Company | Method for cleaning drilling fluid solids from a wellbore using a surfactant composition |
| 5925233, | Oct 15 1996 | Clariant GmbH | Use of alkanesulfonic acids as asphaltene-dispersing agents |
| 5975206, | Mar 31 1998 | BJ SERVICES COMPNAY | Acid gels for fracturing subterranean formations |
| 5977032, | Sep 26 1998 | Atlantic Richfield Company | Acidic surfactant composition and method for cleaning wellbore and flowline surfaces using the surfactant composition |
| 5990072, | Oct 20 1997 | Cognis Corporation | Microemulsion composition for cleaning hard surfaces |
| 5996692, | Feb 13 1998 | ConocoPhillips Company | Surfactant composition and method for cleaning wellbore and oil field surfaces using the surfactant composition |
| 6046140, | Mar 31 1998 | BJ Services Company | Acid gels for fracturing subterranean formations |
| 6090754, | May 11 1995 | ConocoPhillips Company | Surfactant blends for well operation |
| 6110885, | Sep 26 1998 | Atlantic Richfield Company | Acidic surfactant composition and method for cleaning wellbore and flowline surfaces using the surfactant composition |
| 6112814, | Feb 13 1998 | ConocoPhillips Company | Method for cleaning wellbore surfaces using coiled tubing with a surfactant composition |
| 6165946, | Oct 30 1996 | Emery Oleochemicals GmbH | Process for the facilitated waste disposal of working substances based on water-in-oil invert emulsions |
| 6173776, | Oct 03 1995 | Nor Industries, Inc. | Cleaning compositions for oil and gas wells, lines, casings, formations and equipment and methods of use |
| 6191090, | Aug 04 1993 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition based on EO-PO nonionic surfactant |
| 6228830, | Jun 27 2000 | Dotolo Research Ltd. | Heavy oil remover |
| 6260621, | Oct 03 1995 | Nor Industries, Inc. | Process for fracing an oil or gas formation |
| 6302209, | Sep 10 1997 | B J Services Company | Surfactant compositions and uses therefor |
| 6364020, | May 24 1997 | Schlumberger Technology Corporation | Emulsion for well and formation treatment |
| 6486115, | Nov 09 1999 | Baker Hughes Incorporated | Microemulsion cleaning composition |
| 6581687, | Jun 29 1999 | BP Exploration Operating Company Limited | Water-in-oil microemulsions useful for oil field or gas field applications and methods for using the same |
| 6593279, | Dec 10 1999 | SIENA LENDING GROUP LLC | Acid based micro-emulsions |
| 6613720, | Oct 13 2000 | Schlumberger Technology Corporation | Delayed blending of additives in well treatment fluids |
| 6729402, | Jun 14 2000 | CHAMPIONX USA INC | Method of recovering hydrocarbon fluids from a subterranean reservoir |
| 6770603, | Jan 16 1999 | M-I L.L.C. | Electrically conductive non-aqueous wellbore fluids |
| 6793025, | Jan 08 1998 | M-I, L L C | Double emulsion based drilling fluids |
| 6800593, | Jun 19 2002 | TUCC Technology, LLC | Hydrophilic polymer concentrates |
| 6818595, | Feb 14 2001 | SINOMINE RESOURCES US INC | Drilling fluids containing an alkali metal formate |
| 6911417, | Apr 29 2003 | PHILLIPS 66 COMPANY | Water block removal with surfactant based hydrocarbonaceous liquid system |
| 6914040, | May 04 2001 | The Proctor and Gamble Company | Process for treating a lipophilic fluid in the form of a siloxane emulsion |
| 6939832, | Dec 21 1999 | BP Exploration Operating Company Limited | Process for treating an oil well |
| 6984610, | Dec 10 1999 | SIENA LENDING GROUP LLC | Acid based micro-emulsions of surfactants and solvents |
| 7021378, | Dec 31 2003 | CHEVRON U S A INC | Method for enhancing the retention efficiency of treatment chemicals in subterranean formations |
| 7122509, | Apr 08 2004 | PNC Bank, National Association | High temperature foamer formulations for downhole injection |
| 7134496, | Sep 03 2004 | BAKER HUGHES HOLDINGS LLC | Method of removing an invert emulsion filter cake after the drilling process using a single phase microemulsion |
| 7205262, | Dec 12 2001 | LUBRIZOL OILFIELD SOLUTIONS, INC | Friction reducing composition and method |
| 7205264, | Jan 17 2003 | BAKER HUGHES HOLDINGS LLC | Well treatment method using fluid containing lactic acid or salt thereof |
| 7231976, | Nov 10 2004 | BAKER HUGHES, A GE COMPANY, LLC | Method of treating an oil or gas well with biodegradable low toxicity fluid system |
| 7380606, | Mar 01 2002 | Flotek Chemistry, LLC | Composition and process for well cleaning |
| 7392844, | Nov 10 2004 | BAKER HUGHES, A GE COMPANY, LLC | Method of treating an oil or gas well with biodegradable low toxicity fluid system |
| 7407915, | Nov 29 2005 | Baker Hughes Incorporated | Polymer hydration method using microemulsions |
| 7468402, | Mar 17 2004 | BAKER HUGHES HOLDINGS LLC | Polymeric nanoemulsion as drag reducer for multiphase flow |
| 7481273, | Sep 02 2004 | BAKER HUGHES HOLDINGS LLC | Method of using water-in-oil emulsion to remove oil base or synthetic oil base filter cake |
| 7514390, | Dec 28 2004 | ConocoPhillips Company | Method for removing filter cake from a horizontal wellbore using acid foam |
| 7514391, | Dec 28 2004 | ConocoPhillips Company | Method and composition for removing filter cake from a horizontal wellbore using a stable acid foam |
| 7533723, | Oct 09 2003 | Schlumberger Technology Corporation | Well bore treatment fluid |
| 7543644, | Jul 31 2006 | Baker Hughes Incorporated | Concentrated suspension of particulate additives for fracturing and other fluids |
| 7543646, | Jul 31 2006 | SUPERIOR ENERGY SERVICES, L L C | Suspension of concentrated particulate additives containing oil for fracturing and other fluids |
| 7547665, | Apr 29 2005 | Halliburton Energy Services, Inc. | Acidic treatment fluids comprising scleroglucan and/or diutan and associated methods |
| 7552771, | Nov 14 2007 | Halliburton Energy Services, Inc. | Methods to enhance gas production following a relative-permeability-modifier treatment |
| 7559369, | May 10 2007 | Halliubrton Energy Services, Inc.; Halliburton Energy Services, Inc | Well treatment composition and methods utilizing nano-particles |
| 7581594, | Mar 15 2006 | ChemEOR, Inc. | Surfactant method for improved oil recovery from fractured reservoirs |
| 7615516, | Jan 21 2005 | BAKER HUGHES HOLDINGS LLC | Microemulsion containing oil field chemicals useful for oil and gas field applications |
| 7621334, | Apr 29 2005 | Halliburton Energy Services, Inc. | Acidic treatment fluids comprising scleroglucan and/or diutan and associated methods |
| 7622436, | Nov 30 2006 | Colgate-Palmolove Company | Cleaning composition comprising a ternary surfactant system in combination with dipropyl or diisopropyl adipate solvent |
| 7655603, | May 13 2005 | Baker Hughes Incorported; Baker Hughes Incorporated | Clean-up additive for viscoelastic surfactant based fluids |
| 7677311, | Aug 26 2002 | Schlumberger Technology Corporation | Internal breaker for oilfield treatments |
| 7687439, | Sep 03 2004 | BAKER HUGHES HOLDINGS LLC | Method of removing an invert emulsion filter cake after the drilling process using a single phase microemulsion |
| 7709421, | Sep 03 2004 | BAKER HUGHES HOLDINGS LLC | Microemulsions to convert OBM filter cakes to WBM filter cakes having filtration control |
| 7712534, | Mar 14 2008 | Halliburton Energy Services, Inc | Treatment fluids having biocide and friction reducing properties and associated methods |
| 7727936, | Jul 13 2004 | Halliburton Energy Services, Inc.; Halliburton Energy Services, Inc | Acidic treatment fluids comprising xanthan and associated methods |
| 7727937, | Jul 13 2004 | Halliburton Energy Services, Inc.; Halliburton Energy Services, Inc | Acidic treatment fluids comprising xanthan and associated methods |
| 7730958, | Aug 31 2006 | RED DESERT ENTERPRISE, LC | Method and apparatus to enhance hydrocarbon production from wells |
| 7825073, | Jul 13 2004 | Halliburton Energy Services, Inc | Treatment fluids comprising clarified xanthan and associated methods |
| 7833943, | Sep 26 2008 | Halliburton Energy Services, Inc | Microemulsifiers and methods of making and using same |
| 7838467, | Sep 03 2004 | BAKER HUGHES HOLDINGS LLC | Microemulsions to convert OBM filter cakes to WBM filter cakes having filtration control |
| 7846877, | May 20 2009 | Halliburton Energy Services, Inc. | Methods for treating a well using a treatment fluid containing a water-soluble polysaccharide, a water-soluble salt, and urea |
| 7851414, | Jan 21 2005 | BAKER HUGHES HOLDINGS LLC | Microemulsion containing oil field chemicals useful for oil and gas field applications |
| 7855168, | Dec 19 2008 | Schlumberger Technology Corporation | Method and composition for removing filter cake |
| 7857051, | Aug 26 2002 | Schlumberger Technology Corporation | Internal breaker for oilfield treatments |
| 7886824, | Feb 11 2008 | The Lubrizol Corporation | Compositions and methods for gas well treatment |
| 7893010, | May 08 2008 | Schlumberger Technology Corporation | Composition and method for fluid recovery from well |
| 7902123, | Apr 14 2005 | SAS ENVIRONMENTAL SERVICES LIMITED | Microemulsion cleaning composition |
| 7906464, | May 13 2008 | Halliburton Energy Services, Inc | Compositions and methods for the removal of oil-based filtercakes |
| 7910524, | Feb 08 2007 | Halliburton Energy Services, Inc | Treatment fluids comprising diutan and associated methods |
| 7931088, | Jan 29 2009 | Halliburton Energy Services, Inc. | Methods for treating a well by simultaneously introducing into a mixer streams of water, a viscosity-increasing agent, and a particulate and introducing the mixture into the well |
| 7960314, | Sep 26 2008 | Halliburton Energy Services Inc. | Microemulsifiers and methods of making and using same |
| 7960315, | Feb 08 2007 | Halliburton Energy Services, Inc | Treatment fluids comprising diutan and associated methods |
| 7963720, | Sep 26 2007 | Ethical Solutions, LLC | Polymer coated nanoparticle activation of oxidants for remediation and methods of use thereof |
| 7971659, | May 05 2004 | LUBRIZOL OILFIELD SOLUTIONS, INC | Foamer/sulfur scavenger composition and methods for making and using same |
| 7976241, | Mar 27 2006 | Ethical Solutions, LLC | Soil remediation method and composition |
| 7989404, | Feb 11 2008 | The Lubrizol Corporation | Compositions and methods for gas well treatment |
| 7992656, | Jul 09 2009 | Halliburton Energy Services, Inc. | Self healing filter-cake removal system for open hole completions |
| 7998911, | Mar 02 2010 | Oil chem Technologies | Environmental friendly fracturing and stimulation composition and method of using the same |
| 8043996, | Jul 06 2007 | Cleansorb Limited | Method for treatment of underground reservoirs |
| 8053396, | Jun 09 2005 | BASF Aktiengesellschaft | Surfactant mixtures for tertiary oil recovery |
| 8053397, | May 19 2008 | BAKER HUGHES HOLDINGS LLC | Using nanoparticles for water flow control in subterranean formations |
| 8057682, | May 16 2008 | Ethical Solutions, LLC | Green synthesis of nanometals using plant extracts and use thereof |
| 8091644, | Sep 03 2004 | Baker Hughes Incorporated | Microemulsion or in-situ microemulsion for releasing stuck pipe |
| 8091645, | Oct 11 2006 | BAKER HUGHES HOLDINGS LLC | In situ fluid formation for cleaning oil- or synthetic oil-based mud |
| 8091646, | Jul 03 2007 | BAKER HUGHES HOLDINGS LLC | Single phase microemulsions and in situ microemulsions for cleaning formation damage |
| 8100190, | Aug 11 2009 | Halliburton Energy Services, Inc | Methods for swelling swellable elements in a portion of a well using a water-in-oil emulsion |
| 8148303, | Jun 30 2010 | Halliburton Energy Services, Inc | Surfactant additives used to retain producibility while drilling |
| 8183182, | Jul 09 2008 | PETROLEO BRASILEIRO S A - PETROBRAS | Composition of microemulsion and method for advanced recovery of heavy oil |
| 8206062, | Mar 27 2006 | Ethical Solutions, LLC | Soil remediation method and composition |
| 8207096, | Dec 30 2009 | Halliburton Energy Services Inc. | Compressible packer fluids and methods of making and using same |
| 8210263, | Jul 03 2007 | BAKER HUGHES HOLDINGS LLC | Method for changing the wettability of rock formations |
| 8220546, | Feb 11 2008 | The Lubrizol Corporation | Methods for gas well treatment |
| 8227382, | Nov 30 2007 | M-I LLC | Breaker fluids and methods of using the same |
| 8231947, | Nov 16 2005 | Schlumberger Technology Corporation | Oilfield elements having controlled solubility and methods of use |
| 8235120, | Jul 03 2007 | BAKER HUGHES HOLDINGS LLC | Mesophase fluids with extended chain surfactants for downhole treatments |
| 8242059, | Oct 09 2007 | BP Exploration Operating Company Limited | Wellbore fluid |
| 8293687, | Jul 09 2009 | GIFFIN, CLAUDINE | Compositions and processes for fracturing subterranean formations |
| 8342241, | Dec 18 2009 | Schlumberger Technology Corporation | Delivery of nanodispersions below ground |
| 8349771, | Jun 14 2010 | Baker Hughes Incorporated | Method for improving the clean-up of emulsified acid fluid systems |
| 8356667, | Jun 12 2009 | Baker Hughes Incorporated | Liquid crystals for drilling, completion and production fluids |
| 8357639, | Jul 03 2007 | Baker Hughes Incorporated | Nanoemulsions |
| 8372789, | Jan 16 2009 | Halliburton Energy Services, Inc.; Halliburton Energy Services, Inc | Methods of designing treatment fluids based on solid-fluid interactions |
| 8383560, | Aug 07 2009 | S.P.C.M. SA | Method of continuous dissolution of polyacrylamide emulsions for enhanced oil recovery (EOR) |
| 8403051, | Oct 13 2010 | BAKER HUGHES HOLDINGS LLC | Stabilizing emulsified acids for carbonate acidizing |
| 8404623, | Jul 17 2009 | Halliburton Energy Services, Inc. | Stabilization of emulsions containing resinous material for use in the field of oil or gas well treatments |
| 8413721, | May 22 2007 | Halliburton Energy Services, Inc.; Halliburton Energy Services, Inc | Viscosified fluids for remediating subterranean damage |
| 8415279, | Apr 22 2008 | BAKER HUGHES HOLDINGS LLC | Microemulsions used as spacer fluids |
| 8431620, | Mar 31 2006 | ENI S P A ; POLIMERI EUROPA S P A | Process for the preparation of water-in-oil and oil-in-water nanoemulsions |
| 8453741, | Sep 23 2010 | CIES INC | Tethered polymers used to enhance the stability of microemulsion fluids |
| 8499832, | May 13 2004 | BAKER HUGHES HOLDINGS LLC | Re-use of surfactant-containing fluids |
| 8517100, | May 12 2010 | Schlumberger Technology Corporation | Compositions and methods for cleaning a wellbore prior to cementing |
| 8517104, | Mar 22 2010 | S.P.C.M. SA | Process for increasing the transport flow rate of oil from producing wells |
| 8524643, | Jun 09 2005 | BASF SE | Surfactant mixtures for tertiary oil recovery |
| 8551926, | Oct 13 2010 | BAKER HUGHES HOLDINGS LLC | Stabilizing emulsified acids for carbonate acidizing |
| 8592350, | Jun 30 2010 | Halliburton Energy Services, Inc. | Surfactant additives used to retain producibility while drilling |
| 8684079, | Mar 16 2010 | ExxonMobile Upstream Research Company | Use of a solvent and emulsion for in situ oil recovery |
| 8778850, | Oct 24 2012 | Green Earth Technologies, Inc. | Biodegradable non-reactive oil-well stimulation fluid and method of use |
| 8865632, | Nov 10 2008 | PNC Bank, National Association | Drag-reducing copolymer compositions |
| 9068108, | Mar 14 2013 | CESI CHEMICAL INC ; CESI CHEMICAL, INC | Methods and compositions for stimulating the production of hydrocarbons from subterranean formations |
| 9200192, | May 08 2012 | CESI CHEMICAL, INC | Compositions and methods for enhancement of production of liquid and gaseous hydrocarbons |
| 9222013, | Nov 13 2008 | PNC Bank, National Association | Water-in-oil microemulsions for oilfield applications |
| 20010007663, | |||
| 20030022944, | |||
| 20030069143, | |||
| 20030166472, | |||
| 20030232095, | |||
| 20060014648, | |||
| 20060211593, | |||
| 20060258541, | |||
| 20070123445, | |||
| 20070293404, | |||
| 20070295368, | |||
| 20080274918, | |||
| 20080287324, | |||
| 20090078415, | |||
| 20090137432, | |||
| 20090159288, | |||
| 20090221456, | |||
| 20090260819, | |||
| 20090275488, | |||
| 20090281004, | |||
| 20100022421, | |||
| 20100173805, | |||
| 20100216670, | |||
| 20100243248, | |||
| 20100252267, | |||
| 20100263863, | |||
| 20100272765, | |||
| 20100307757, | |||
| 20110021386, | |||
| 20110136706, | |||
| 20110146983, | |||
| 20110190174, | |||
| 20110220353, | |||
| 20110237467, | |||
| 20110253365, | |||
| 20110290491, | |||
| 20120004146, | |||
| 20120015852, | |||
| 20120071366, | |||
| 20120080232, | |||
| 20120129738, | |||
| 20120149626, | |||
| 20120168165, | |||
| 20120181019, | |||
| 20120193095, | |||
| 20120208726, | |||
| 20120234548, | |||
| 20120241155, | |||
| 20120241220, | |||
| 20120255887, | |||
| 20120261120, | |||
| 20120285690, | |||
| 20120285694, | |||
| 20120318504, | |||
| 20120318515, | |||
| 20120322697, | |||
| 20120325492, | |||
| 20130029883, | |||
| 20130048281, | |||
| 20130079255, | |||
| 20130109597, | |||
| 20130133886, | |||
| 20130137611, | |||
| 20130146288, | |||
| 20130146545, | |||
| 20130153232, | |||
| 20130153234, | |||
| 20130192826, | |||
| 20130233559, | |||
| 20130244913, | |||
| 20130261033, | |||
| 20130292121, | |||
| 20140005079, | |||
| 20140110344, | |||
| 20140202700, | |||
| 20140262274, | |||
| 20140262288, | |||
| 20140284057, | |||
| 20140332212, | |||
| 20140367107, | |||
| 20150105302, | |||
| 20150247082, | |||
| 20150247381, | |||
| 20150329767, | |||
| 20160003018, | |||
| 20160017204, | |||
| 20160024891, | |||
| 20160032172, | |||
| CA2345305, | |||
| CN102127414, | |||
| CN102277143, | |||
| CN103614128, | |||
| CN103642477, | |||
| CN2394858, | |||
| EP1051237, | |||
| EP1378554, | |||
| EP1786879, | |||
| EP1880081, | |||
| EP2195400, | |||
| WO1999049182, | |||
| WO2005048706, | |||
| WO2007011475, | |||
| WO2012158645, |
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